Computer-aided design of chiral ligands. Part III. A novel ligand for asymmetric allylation designed using computational techniques

[reaction: see text] Computer-aided design protocols to identify new chiral ligands for reactions proceeding through well-defined transition states are outlined. Ligand families are discovered via computational screening of large structural databases such as the Cambridge Structural Database. Using this method, a novel cis-decalin ligand has been identified as a chiral auxiliary for the allylboration of aldehydes. Synthesis, resolution, and evaluation revealed that this new auxiliary provided the aldehyde facial approach upon which the design was predicated.     

Synthesis of cyclosporin A-derived affinity reagents by olefin metathesis

[reaction: see text] New affinity reagents were synthesized using alkene metathesis to directly modify the MeBmt side chain of cyclosporin A. The reagents were used to detect novel cyclophilins from cellular extracts.     

Pseudotetrahedral polyhaloadamantanes as chirality probes: synthesis,separation, and absolute configuration

Pseudotetrahedral, conformationally as well as configurationally stable 1-bromo-3-chloro-5-fluoro- (4) and 1-bromo-3-chloro-5-fluoro-7-iodoadamantane (5) (and some related compounds) were prepared by our recently devised phase-transfer catalytic halogenation protocol; the optical antipodes of 4 were separated by HPLC on chiral phase in ee > 99%, and the absolute configurations were assigned by matching observed and computed circular dichroism spectra. Structure 5 is the first chiral aliphatic hydrocarbon containing all stable (nonradioactive) halogens; its structure was proven by NMR spectroscopy and by X-ray crystal data. We emphasize that the combination of experiment and theory is very powerful in assigning absolute configurations even for molecules without typical chromophors, with small values for the optical rotation, and without an atom at the stereogenic center.     

Spontaneous assembly of a hydrogen-bonded tetrahedron

Triphenylamine ortho-tricarboxylic acid (1) has been synthesized and the crystal structure reported. This molecule is shown to spontaneously self-assemble into a hydrogen-bonded tetrahedron. Furthermore, Electrospray Ionization Mass Spectroscopy shows evidence for the stability of such aggregates from an ethanol/water solution.     

Spectroscopic evidence of polymorphism in vitreous B2O3

Brillouin and Raman spectroscopy were performed on B2O3 glass compressed to 57 GPa at 273 K. Upon compression the sound velocities increase smoothly and the boroxol ring Raman mode vanishes by 11 GPa. Upon decompression the sound velocities follow a different path and at 3 GPa a discontinuity of 3 km/s in V(p) and 2 km/s in V(s) returns the velocities to the values seen on compression. After the transition, the boroxol ring Raman mode reappears. A second pressure cycle produces the same behavior, suggesting the 3 GPa transition occurs between vitreous polymorphs with different boron coordination.     

The influence of chiral auxiliaries and catalysts on the selectivity of intramolecular conjugate additions of pyrrole to N-tethered Michael acceptors

A series of pyrroles incorporating N-tethered acrylates and related groups has been prepared and examined for their capacity to undergo intramolecular Michael addition reactions to form, in a diastereo- or enantio-selective fashion, the corresponding 8-substituted tetrahydroindolizidine or homologues thereof.     

Unsaturated 1,2-amino alcohols and ethers from aziridines and organolithiums

Organolithium-induced ring-opening of aziridines of 2,5-dihydrofuran (5 and 8) and 1,4-dimethoxybut-2-ene (16, 17 and 23) gives 3-substituted 2-aminobut-3-en-1-ols 9-15 and amino ethers 18-20 and 24-26.     

An outer-sphere ligand for uranyl carbonate

A novel supramolecular host for the uranyl carbonate complex has been designed and synthesized. The modified cyclodextrin host binds uranyl carbonate in water with a stability of 253 M(-1).